Effects of hydrogen on the anodic behavior of Alloy 690 at 60 °C

Polarization and electrochemical impedance spectroscopy (EIS) measurements, Mott-Schottky (M-S) analysis and X-ray photoelectron spectroscopy (XPS) were used to investigate the effects of hydrogen on the anodic behavior of a one-dimensionally (1D) 25% cold worked (CW) Alloy 690 thermal treated (TT) in a boric acid and sodium sulphate solution at 60 °C. The pre-hydrogen-charged specimen exhibited a higher anodic current than that of the uncharged specimen below the transpassive potential. The charged hydrogen can be trapped in the metal. Electrochemical impedance spectroscopy (EIS) showed that the resistance capacitance loop of the hydrogen-charged specimen was significantly smaller than that of the uncharged specimen. Mott-Schottky analyses indicated that the passive film formed on Alloy 690 at −0.2 V_SCE was an n-type semiconductor, with a p-n hetero-junction at 0.2 V_SCE. Charged hydrogen increased the carrier density and the thickness of the passive film both at −0.2 V_SCE and 0.2 V_SCE. The Ni/Cr ratio in the surface film decreased after hydrogen charging, indicating that charged hydrogen could enhance the oxide film growth by increasing the OH⁻ (O²⁻) concentrations through its reaction with vacancies.     

The effect of cysteine on the corrosion of 304L stainless steel in sulphuric acid

The effect of cysteine on the corrosion of 304L stainless steel in 1 mol l⁻¹ H₂SO₄ was studied using open-circuit potential measurements, anodic polarization curves, electrochemical impedance spectroscopy (EIS) and scanning electron microscopy (SEM). All the electrochemical measurements obtained in the presence of low cysteine concentration (10⁻⁶-10⁻⁵ mol l⁻¹) presented the same behaviour as those obtained in the absence of cysteine, a passivated steel surface. However, for higher cysteine concentrations (10⁻⁴-10⁻² mol l⁻¹), a different behaviour was observed: the corrosion potential stabilized at a more negative value; an active region was observed in the anodic polarization curves and the electrochemical impedance diagrams showed an inductive loop at lower frequencies and a much lower polarization resistance. These results show that the presence of cysteine at high concentration turns the surface of 304L stainless steel electrochemically active, probably dissolving the passivation layer and promoting the stainless steel anodic dissolution. SEM experiments performed after immersion experiments at corrosion potential were in good agreement with the electrochemical results.     

Evaluation of metastable pitting on titanium by charge integration of current transients

The metastable pitting of titanium has been studied under potentiostatic control in solutions containing chloride ions. An approach based on the charge integration of current transients was proposed for a quantitative determination of metastable pitting. A pit density (d_mpit) was defined as the number of metastable pits per unit area per unit time (cm⁻² h⁻¹) with a typical size, instead of a size distribution. The calculated d_mpit of titanium at 0.5 V_SCE in 0.6 M NaCl was about 1.0 × 10³ cm⁻² h⁻¹ with a typical radius of 0.12 μm. An exponential potential dependence of d_mpit was obtained through the integration approach.     

Improvement on the pitting corrosion resistance of 304 stainless steel via duplex passivation treatment

A remarkable improvement in the pitting corrosion resistance of 304 stainless steel was attempted using a novel duplex passivation treatment method. First, chemical passivation in nitric acid followed electrochemical passivation via potential polarization of step cycling in sodium nitrate electrolyte. Compared with traditional chemical passivation, breakdown potential was increased from 0.31 V_SCE to positive than 0.9 V_SCE at 70°C in a solution bearing 0.6 M [Cl^?] concentration. The critical pitting temperature was enhanced from 21.5°C to above 70°C in a solution with 6 M [Cl^?] concentration. Impedance analysis and X‐ray photoelectron spectroscopy results show that a more compact passive film with a higher ratio of chromium oxide on iron oxide was achieved by electrochemical passivation compared with chemical passivation. Morphology observation suggested that the potential polarization of step cycling slightly increased the dissolution of inclusions after being subjected to chemical passivation. The probable reason for the improvement on pitting resistance is discussed in detail based on inclusion dissolution and the protectiveness in passive film.     

Optimization of the pulsed current gas tungsten arc welding (PCGTAW) parameters for corrosion resistance of super duplex stainless steel (UNS S32760) welds using the Taguchi method

In the present work, a design of experiment (DOE) technique, the Taguchi method, has been used to optimize the pulsed current gas tungsten arc welding (PCGTAW) parameters for the corrosion resistance of super duplex stainless steel (UNS S32760) welds. A L₉ (3⁴) orthogonal array (OA) of Taguchi design which involves nine experiments for four parameters (pulse current, background current, % on time, pulse frequency) with three levels was used. Corrosion resistance in 3.5%NaCl solution was evaluated by anodic polarization tests at room temperature. Analysis of variance (ANOVA) is performed on the measured data and S/N (signal to noise) ratios. The higher the better response category was selected to obtain optimum conditions. The optimum conditions providing the highest pitting potential were estimated. The optimum conditions were found as the second level of pulse current (120 A), second level of background current (60 A), third level of % on time (80) and third level of pulse frequency (5 Hz). Under these conditions, pitting potential was predicted as 1.04 V_SCE that was very close to the observed value of 1.06 V_SCE. As a result of Taguchi analysis in this study, the pulse current was the most influencing parameter on the corrosion resistance and the background current had the next most significant effect. The percentage contributions of pulse current, background current, % on time, and pulse frequency to the corrosion resistance are 66.28%, 25.97%, 2.71% and 5.04%, respectively. Consequently, the Taguchi method was found to be promising technique to obtain the optimum conditions for such studies. Moreover, the experimental results obtained confirm the adequacy and effectiveness of this approach.     

Corrosion resistance of TiO2 films grown on stainless steel by atomic layer deposition

Titanium dioxide (TiO₂) films have been deposited onto stainless steel substrates using atomic layer deposition (ALD) technique. Composition analysis shows that the films shield the substrates entirely. The TiO₂ films are amorphous in structure as characterized by X-ray diffraction. The electrochemical measurements show that the equilibrium corrosion potential positively shifts from − 0.96 eV for bare stainless steel to − 0.63 eV for TiO₂ coated stainless steel, and the corrosion current density decreases from 7.0 × 10^− 7 A/cm² to 6.3 × 10^− 8 A/cm². The corrosion resistance obtained by fitting the impedance spectra also reveals that the TiO₂ films provide good protection for stainless steel against corrosion in sodium chloride solution. The above results indicate that TiO₂ films deposited by ALD are effective in protecting stainless steel from corrosion.     

Improvement of the cavitation erosion resistance of UNS S31803 stainless steel by duplex treatment

A duplex surface treatment consisting of High Temperature Gas Nitriding (HTGN) followed by Low Temperature Plasma Nitriding (LTPN) was carried out in an UNS S31803 duplex stainless steel. The HTGN treatment was intended to produce a relatively thick and hard fully austenitic layer giving mechanical support to the thinner and much harder expanded austenite layer. HTGN was performed at 1200 °C for 3 h, in a 0.1 MPa N₂ atmosphere while LTPN, was carried out in a 75% N₂ + 25% H₂ atmosphere, at 400 °C for 12 h, under a 250 Pa pressure, and 450 V. An expanded austenite γ_N layer, 2.3 μm thick, 1500 HV0.025 hard, was formed on top of a 100 μm thick, 330 HV 0.1 hard, fully austenitic layer, containing 0.9 wt% N. For comparison purposes LTPN was carried out with UNS S30403 stainless steel specimens obtaining a 4.0 μm thick, 1500 HV 0.025 hard, expanded austenite layer formed on top of a fully austenitic matrix having 190 HV 0.1. The nitrided specimens were tested in a 20 kHz vibratory cavitation-erosion testing equipment. Comparison between the duplex treated UNS S31803 steel and the low temperature plasma nitrided UNS S30403 steel, resulted in incubation times almost 9 times greater. The maximum cavitation wear rate of the LTPN UNS S30403 was 5.5 g/m²h, 180 times greater than the one measured for the duplex treated UNS S31803 steel. The greater cavitation wear resistance of the duplex treated UNS S31803 steel, compared to the LTPN treated UNS S30403 steel was explained by the greater mechanical support the fully austenitic, 330 HV 0.1 hard, 100 μm layer gives to the expanded austenite layer formed on top of the specimen after LTPN. A strong crystallographic textured surface, inherited from the fully austenitic layer formed during HTGN, with the expanded austenite layer showing {101} crystallographic planes//surface contributed also to improve the cavitation resistance o f the duplex treated steel.     

Comprehensive model for the activation mechanism of Al-Zn alloys produced by indium

Exploratory work on the electrochemical behaviour of the Al-4%Zn alloy in the presence of In³⁺ in weakly acid chloride and acetic media is reported. It was found that in chloride solutions, active dissolution takes place at very negative potentials (−1.5 V_SCE). This significative enhancement in the electrochemical activity of the alloy is described and discussed. The aim of this paper is to explain the relationship between the operating potential (−1.1 V_SCE) given by the commercial alloy (basically an Al-Zn-In alloy), its high efficiency, its quasi-uniform attack observed and the enhanced activity found (−1.5 V_SCE). An unified model that explains this findings and the activation process of pure Al by In³⁺ is proposed. It was found that two activation mechanism are operative on Al: (i) When sufficient amount of In at the interface in quasi-liquid state is present, an In-Al amalgam is responsible for the activation process (−1.5 V_SCE). This process is favoured by Zn reach zones that favours In enrichment at the interface by displacement reaction. (ii) At higher anodic potentials (near −1.2 V_SCE), the presence of In at the interface facilitates a chloride adsorption process which depolarised the anodic reaction.     

Passivity of 316L stainless steel in borate buffer solution studied by Mott-Schottky analysis, atomic absorption spectrometry and X-ray photoelectron spectroscopy

The passivity of 316L stainless steel in borate buffer solution has been investigated by Mott-Schottky, atomic absorption spectrometry (AAS) and X-ray photoelectron spectroscopy (XPS). The results indicate that the polarization curve in the passive region possesses several turning potentials (0 V_SCE, 0.2 V_SCE, 0.4 V_SCE, 0.6 V_SCE and 0.85 V_SCE). The passive films formed at turning potentials perform different electrochemical and semiconductor properties. Further, the compositions of the passive films formed at turning potentials are investigated. The results reasonably explain why these potentials appear in the passive region and why specimens perform different properties at turning potentials.     

Metal release from various grades of stainless steel exposed to synthetic body fluids

Release rates of individual alloy constituents have been determined from seven grades of stainless steels exposed to two synthetic body fluids, used as surrogates for different areas of potential exposure in the lung: “Gamble’s solution”, (pH 7.4) that represents the interstitial fluid of the deep lung, and artificial lysosomal fluid (ALF) that represents the more acidic (pH 4.5-5) milieu of particles following their phagocytosis by macrophages. Total metal release rates from all grades of stainless steel investigated were low (<5 μg cm⁻² week⁻¹). The more acidic environment of ALF resulted in significantly higher total metal release rates (0.3-4.6 μg cm⁻² week⁻¹) compared to Gamble’s solution (<0.1 μg cm⁻² week⁻¹).     

H2S and O2 influence on the corrosion of carbon steel immersed in a solution containing 3 M diethanolamine

Aqueous solutions with 3 mol L⁻¹ (M) diethanolamine (DEA) concentration are extensively used in the gas processing industry to remove acid gases. However, the degradation of the DEA and the formation of heat-stable salts (HSS) lead to severe corrosion problems. Even worse, equipment corrosion can be magnified by the unavoidable presence of sulphide acid and dissolved oxygen as a result of hydrocarbon (natural gases and crude oil) processing. The aim of this work is to study the combined corrosion effects of DEA, sulphide acid and oxygen on carbon steel. Electrochemical methods revealed that in the 3 M DEA medium without oxygen, corrosion processes are modulated by adsorbed DEA film formation. Furthermore, it was shown that the addition of oxygen and 15 × 10⁻³ mol L⁻¹ (15 mM) H₂S produced the formation of an adherent film on the carbon steel surface. Chemical analyses by EDAX revealed a homogeneous film of corrosion products composed of iron oxide and sulphide formed in DEA solution containing O₂ and H₂S, respectively. Equivalent circuits were used to estimate the parameters associated with ion diffusion through the formed corrosion films. The results showed that the presence of H₂S induced the formation of thin iron sulphide films that provide protective properties to the metal. It is concluded that the presence of oxygen in a sweetening plant should be avoided as DEA degradation can be produced with the subsequent decrease in chelating process efficiency and the increase in corrosion problems.     

Oxidation of stainless steel 304L in carbon dioxide

Oxidation of 304L stainless steel in a carbon dioxide atmosphere at 10⁵ Pa has been studied. Between 1193 and 1293 K the oxidation kinetics exhibit first a rapid increase, then a parabolic behaviour with apparent activation energy of (209 ± 8) kJ mol⁻¹ and obeys a Langmuir pressure law. After 1.15 mg cm⁻², the kinetics become almost linear.The reaction products are chromia at the grain boundaries, wüstite (Fe_1−xO) on the surface for weight gains greater than 0.30 mg cm⁻² and chromite. The very complex reaction mechanism takes into account random buckling for weight gains >1.15 mg cm⁻².     

Sintered stainless steels: Fatigue crack propagation resistance under hydrogen charging conditions

Monophasic and multiphasic (two and three phases) sintered stainless steels were prepared both considering premixes of AISI 316LHC and AISI 434LHC stainless steels powders and using a prealloyed duplex stainless steel 25% Cr, 5% Ni, 2% Mo powder. Their fatigue crack propagation resistance was investigated both in air and under hydrogen charging conditions (0.5 M H₂SO₄ + 0.01 M KSCN aqueous solution; applied potential = −700 mV/SCE), considering three different stress ratios (R = 0.1; 0.5; 0.75). Fatigue crack propagation micromechanisms were investigated by means of fracture surface scanning electron microscope (SEM) analysis.For all the investigated sintered stainless, fatigue crack propagation resistance is influenced by hydrogen charging and an increase of crack growth rates dependent on the steel microstructure is obtained. Experimental results also allow to identify the sintered stainless steel obtained from the prealloyed 25% Cr, 5% Ni, 2% Mo powder as the most resistant to fatigue crack propagation in air and under hydrogen charging conditions.     

304L stainless steel oxidation in carbon dioxide: An XPS study

From the early beginning of the oxidation of 304L stainless steel in carbon dioxide at 1273 K (1 min, for a weight gain of 0.02 mg cm⁻²), the surface of the alloy was entirely covered by oxides: magnetite Fe₃O₄, chromia Cr₂O₃ and traces of wüstite Fe_1−xO. Later on, for weight gains approaching 1 mg cm⁻², magnetite remained at the outer interface, with traces of hematite (Fe₂O₃), above a thick layer of wüstite Fe_1−xO. Magnetite and wüstite may favour adhesion of thermal plasma protective coatings such as alumina.     

Electronic properties of Al/DNA/p-Si MIS diode: Application as temperature sensor

The current-voltage (I-V) measurements were performed in the temperature range (200-300 K) on Al/DNA/p-Si Schottky barrier type diodes. The Schottky diode shows non-ideal I-V behaviour with ideality factors n equal to 1.34 ± 0.02 and 1.70 ± 0.02 at 300 K and 200 K, respectively, and is thought to have a metal-interface layer-semiconductor (MIS) configuration. The zero-bias barrier height Φ_b determined from the I-V measurements was 0.75 ± 0.01 eV at 300 K and decreases to 0.61 ± 0.01 eV at 200 K. The forward voltage-temperature (V_F-T) characteristics were obtained from the I-V measurements in the temperature range 200-300 K at different activation currents (I_F) in the range 20 nA-6 μA. The V_F-T characteristics were linear for three activation currents in the diode. From the V_F-T characteristics at 20 nA, 100 nA and 6 μA, the values of the temperature coefficients of the forward bias voltage (dV_F/dT) for the diode were determined as −2.30 mV K⁻¹, −2.60 mV K⁻¹ and −3.26 mV K⁻¹ with a standard error of 0.05 mV K⁻¹, respectively.     

Synthesis of vanadium oxide, V6O13 hollow-flowers materials and their application in electrochemical supercapacitors

Hollow flowers-like V₆O₁₃ with an average size of 3 μm was successfully synthesized via a facile sol-hydrothermal approach in a short time. The surface composition, crystalline components and morphology of V₆O₁₃ were characterized by X-ray photoelectron spectra (XPS), powder X-ray diffraction (XRD) and scanning electron microscopy (SEM) measurements, respectively. An intercalating-exfoliating-self-assembly model was proposed to explain the formation process of hollow-flower structure based on experimental results. The obtained hollow flowers-like V₆O₁₃ exhibits high specific capacitance, good cyclability and low resistance as revealed by analysis of cyclic voltammetry (CV), galvanostatic charge/discharge and electrochemical impedance spectroscopy (EIS). Experimental results also indicate that hollow flowers-like V₆O₁₃ can deliver a capacitance of 417 F g⁻¹ at a scan rate of 5 mV s⁻¹. This value would decrease to 400 F g⁻¹ after 1000 cycles in potential range from 0 to 0.8 V versus saturated calomel electrode (SCE) in 1 mol L⁻¹ NaNO₃ aqueous electrolyte at pH of 2.     

Electrochemically deposited polypyrrole films and their characterization

Ionically conductive polypyrrole films have been deposited at 295 K from anhydrous acetonitrile, acetonitrile/H₂O and NaBF₄ aqueous solutions onto platinum, mild steel and stainless steel discs, using cyclic voltammetry, potentiostatic and galvanostatic techniques. Cyclic voltammetry of the polymer films has been studied as a function of water content of the acetonitrile solvent, polypyrrole concentration and potential sweep rate. Potentiostatic growth of thicker (< 30 micron) films on stainless steel allowed free-standing polypyrrole membranes to be produced. Well adherent and conductive films were deposited at constant potential in stirred solutions from acetonitrile electrolytes containing 1% (v/v) of water. The membrane resistivity of the reduced films in 0.5 mol dm^− 3 KCl_(aq) at 295 K was ≈ 1 × 10⁶ Ω cm, while the resistivity of the oxidised membrane was 2700 Ω cm.     

Depassivation-repassivation behavior of type-312L stainless steel in NaCl solution investigated by the micro-indentation

Repassivation behavior of type-312L stainless steel containing 6% of molybdenum was examined in NaCl solution using in situ micro-indentation technique, together with type-304 and 316L stainless steels. High stability of the passive film formed on the type-312L stainless steel was also examined by depth profiling analysis of passive films using glow discharge optical emission spectroscopy (GDOES). In 0.9 mol dm⁻³ NaCl solution at 296 K the type-304 and 316L stainless steels are passive only up to 0.3 V (SHE), above which pitting corrosion occurs. In contrast, no pitting corrosion occurs on type-312L stainless steel. Despite the significant difference of the pitting corrosion resistance, the repassivation kinetics of the three stainless steels, examined by micro-indentation at 0.3 V (SHE), is similar. The presence of molybdenum in the stainless steel does not influence the repassivation kinetics. The charge required to repassivate the ruptured type-312L stainless steel surface increases approximately linearly with the potential, even though the passivity-maintaining current increased markedly at potentials close to the transpassive region. Repassivation occurs without accompanying significant dissolution of steel, regardless of the stability of passive state. Depth profiling analyses of the passive films on the type-312L stainless steels formed at several potentials revealed that molybdenum species enrich in the outer layer of the passive film, below which chromium-enriched layer is present. The permeation of chloride ions may be impeded by the outer layer containing molybdate, enhancing the resistance against the localized corrosion of the type-312L stainless steel.     

The electroplated palladium-copper alloy film on 316L stainless steel and its corrosion resistance in mixture of acetic and formic acids

Palladium-copper alloy films (Cu 2.93-5.66 at.%) were deposited on 316L stainless steel by electroplating. The films showed good adhesive strength and increased surface micro-hardness. In boiling mixture of 90% acetic acid + 10% formic acid + 400 ppm Br⁻ under stirring (625 r/min), the Pd-Cu films showed better corrosion resistance than Pd film. The Pd-5.66%Cu films showed the lowest corrosion rate almost three orders of magnitude lower than that of 316L matrix. The increased corrosion resistance of Pd-Cu films was attributed to the improved passivity, better barrier effect, increased surface hardness and the effect of Cu to resist pitting.     

Cathodic reduction of the duplex oxide films formed on copper in air with high relative humidity at 60 °C

The cathodic reduction of duplex air-formed oxide film on copper was performed at a constant current density of i_c = −50 μA cm⁻² in deaerated 0.1 M KCl solution to investigate the sequence of cathodic reduction of each oxide layer and its mechanism. The single-phase thick CuO film on copper was also cathodically reduced at i_c = −50 μA cm⁻² or −2.5 mA cm⁻². The surface characterizations of the air-formed oxide film and single-phase CuO film before cathodic reduction and after partial or complete cathodic reduction were performed by XPS and X-ray diffraction, respectively.The two plateau regions appeared in the potential vs. time curve during cathodic reduction of the duplex air-formed oxide film on copper, while one plateau region was observed in the potential-time curve during cathodic reduction of the single-phase CuO film on copper. The potential in the first plateau region for the air-formed film coincided with that in the plateau region for the CuO film. The results of XPS and X-ray diffraction suggested that in the first plateau region, the outer CuO layer is directly reduced to metallic Cu, while in the second plateau region, the inner Cu₂O layer is reduced to metallic Cu.